1. Field of the Invention
The present invention relates to polymer-containing compositions useful in a variety of cleaning applications, including laundering of textiles, fabrics and clothing, and hard surface cleaning including dishwashing. The present invention provides detergent compositions, essentially free of peroxygen or chlorine bleach compounds, containing one or more surfactants, one or more builders, one or more enzymes and one or more low molecular weight (e.g., 0.8-25 kDa) polyethyleneimine (PEI) polymers or salts thereof, and methods of producing such compositions. The compositions of the invention provide certain benefits in cleaning of textiles (particularly fabrics including clothing), hard surfaces and dishware and utensils, including enhanced removal of certain difficult-to-remove stains such as chocolate pudding and grass, as well as of polyphenolic stains such as cherry juice, blueberry juice, red wine, tea and coffee. The invention also provides methods of using these compositions in laundry, hard surface cleaning and dishwashing applications.
2. Related Art
Recently, in some geographical areas, governmental bodies have restricted the phosphorus content of detergent compositions, necessitating the formulation of laundry detergents containing chelants less effective than the conventionally used phosphonates or polyphosphonates. These requirements have complicated the formulation of effective and appropriately priced laundry detergent compositions. It would, therefore, be highly desirable to be able to formulate detergent compositions substantially free of peroxygen or chlorine bleach compounds which contain reduced levels of phosphorous-containing components, but still exhibit excellent cleaning and stain removal performance.
Moreover, there are a number of frequently encountered stains that are often very difficult to remove from clothing and other fabrics, and other household surfaces and items such as dishware, regardless of whether or not the detergent formulation used contains phosphorous-containing compounds. Such stains include, for example, polyphenolic-based stains such as cherry juice, blueberry juice and red wine, along with tea, coffee and chocolate pudding. The challenge of removing such stains from clothing has also made it difficult to formulate laundry detergent compositions that are effective at removing such stains while avoiding harm to clothing and other household fabrics and surfaces (including dishware), at a reasonable price point. It would, therefore, be highly desirable to be able to formulate detergent compositions that exhibit excellent cleaning and stain removal performance on a variety of difficult-to-remove stain types that do not result in damage to the household items on which the compositions are used.
Art-known approaches to these problems have included the use of polyethyleneimine (PEI) polymers to enhance stain removal. PEI polymers are also known in the art as sequestrants in a variety of contexts.
U.S. Pat. No. 3,033,746 to Moyle et al. discloses compositions comprising PEI for use in coating, oil/latex paint and cellulosic applications. The compositions are said to have improved antimicrobial properties by combining halophenol compounds with PEI.
WO 94/27621 to Mandeville discloses a method of reducing iron absorption from the gastrointestinal tract by orally administering a therapeutic amount of PEI.
U.S. Pat. No. 4,085,060 to Vassileff discloses sequestering compositions for industrial applications comprising polycarboxylate polymers and PEI which have excellent sequestering properties for metals.
U.S. Pat. No. 3,636,213 to Gerstein discloses a method for solubilizing heavy metal salts of 1-hydroxy-2-pyridinethione in cosmetic formulations where PEI functions as a solubilizing agent.
U.S. Pat. No. 3,400,198 to Lang discloses wave set retention shampoo compositions containing PEI. The compositions are said to precipitate on the hair fiber when diluted with water in the course of usage. Upon drying, PEI improves the wave retention of the hair as well as improving hair manageability. No builders or enzymes are present in such compositions.
U.S. Pat. No. 3,740,422 to Hewitt and U.S. Pat. No. 3,769,398 to Hewitt disclose aqueous and aqueous alcoholic scalp rinses containing solubilized PEI. It is said that PEI is effective against Pityrosporum ovale, the fungus believed to be associated with dandruff and therefore PEI serves as an anti-dandruff agent. No builders or enzymes would be present in such compositions.
British Patent No. 1,524,966 (to Reckitt and Colman Products) and British Patent No. 1,559,823 (to Reckitt and Colman Products) disclose anti-dandruff shampoo compositions comprising PEI as a conditioning agent for hair and as an antimicrobial agent. Again, no detergency builders or enzymes would be present in such compositions.
U.S. Pat. No. 5,360,581 to Rizvi et al. and U.S. Pat. No. 5,417,965 to Janchitraponvej et al. disclose conditioning shampoo compositions containing PEI. It is said that protonated PEIs with cationic polyquaternium 32 provide improved stability and conditioning benefits. No detergency builders or enzymes would be present in such compositions.
U.S. Pat. No. 3,251,778 to Dickson et al., U.S. Pat. No. 3,259,512 to Dickson et al. and U.S. Pat. No. 3,271,307 to Dickson et al. disclose processes for preparing PEIs and derivatives thereof. It is suggested that PEIs can be broadly used in various applications such as oil well treatment, asphalt applications, textile applications and the like.
U.S. Pat. No. 5,259,984 to Hull discloses a rinse free cleaner composition for hands, upholstery and carpet containing PEI.
U.S. Pat. No. 2,182,306 to Ulrich, U.S. Pat. No. 2,208,095 to Esselmann, U.S. Pat. No. 2,553,696 to Wilson, U.S. Pat. No. 2,806,839 to Crowther and U.S. Pat. No. 3,627,687 to Teumac et al. disclose methods of preparing various PEIs.
U.S. Pat. No. 3,844,952 to Booth discloses detergent and fabric softener compositions containing alkylated and alkanoylated PEIs as antistatic agents. The alkylated or alkanoylated polyethyleneimines disclosed by Booth differ structurally from the polyethyleneimines and polyethyleneimine salts (or mixtures) of the invention which are not derivatized.
Furthermore, there are numerous patents that describe various alkoxylated derivatives of PEI (similar to those described by Booth) which are also structurally very different and are otherwise unrelated to the present invention. See for example, U.S. Pat. Nos. 2,792,372, 4,171,278, 4,341,716, 4,597,898, 4,561,991, 4,664,848, 4,689,167 and 4,891,160.
Finally, perhaps the most relevant references that do disclose the use of polyethyleneimines in detergent compositions are as follows.
U.S. Pat. No. 3,489,686 to Parran, for example, discloses detergent compositions containing certain PEIs which serve to enhance deposition and retention of particulate substances and surfaces washed with such compositions. There is no teaching or suggestion that polyethyleneimines be used in compositions substantially free of enzymes.
AU Patent No. 17813/95 (to Procter & Gamble) and JP 08,053,698 (to Procter & Gamble) disclose detergent compositions containing 0.01% to 10% PEI substantially free of tertiary amino groups having a specific molecular weight of 100-600 as a polymeric chlorine scavenger. The compositions are said to minimize fading of fabric colors sensitive to chlorine which may be present in the composition or in the wash or rinse water. The compositions optionally contain peroxygen or chlorine bleaching agents.
U.S. Pat. No. 5,858,948 to Ghosh et al. (and currently owned by Procter & Gamble) discloses liquid laundry detergent formulations that provide enhanced hydrophilic soil cleaning benefits, comprising 0.01 to 20% by weight of a zwitterionic polymer which comprises a polyamine backbone, particularly wherein the degree of quaternization of the polyamine backbone is controlled. However, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
U.S. Pat. No. 5,904,735 to Gutierrez et al. (and currently owned by The Sun Products Corporation) discloses detergent compositions, essentially free of peroxygen or chlorine bleach compounds, that comprised from about 0.001% to about 5% by weight of PEIs or salts thereof, and the use of such compositions in enhanced removal of organic stains, particularly polyphenolic stains such as morello juice (cherry juice), blueberry juice, red wine, tea and coffee, as well as grass. However, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
U.S. Pat. No. 5,955,415 to Gutierrez et al. (and currently owned by The Sun Products Corporation), discloses detergent compositions containing peroxygen or chlorine bleach compounds and from about 0.001% to about 5% by weight of PEIs or salts thereof. These compositions exhibit controlled and improved bleaching action on stains as well as improved storage stability, fabric safety and whitening/brightening characteristics. However, this reference did not disclose the use of PEIs in detergent compositions free or essentially free of peroxygen or chlorine bleach compounds. Moreover, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
U.S. Pat. No. 5,968,893 to Manohar et al. (and currently owned by Procter and Gamble) discloses laundry detergent compositions that provide soil release benefits to fabrics, comprising modified polyamine soil release agents such as modified polyamines having functionalized backbone moieties. Such compositions provided improved stability towards bleach. However, this reference did not disclose the use of PEIs in detergent compositions free or essentially free of peroxygen or chlorine bleach compounds. Moreover, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
U.S. Pat. No. 6,071,871 to Gosselink et al. (and currently owned by Procter and Gamble) discloses laundry detergent compositions that provide soil release benefits to fabrics, comprising modified polyamine soil release agents such as modified polyamines having functionalized backbone moieties. Such compositions provided improved stability towards bleach. However, this reference did not disclose the use of PEIs in detergent compositions free or essentially free of peroxygen or chlorine bleach compounds. Moreover, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
U.S. Pat. No. 6,340,661 to van Deurzen et al. (and currently owned by Unilever Home and Personal Care), discloses bleaching compositions for laundry fabrics, comprising a bleach catalyst comprising: (a) a ligand which forms a complex with a transition metal and which complex catalyzes the bleaching of stains in the absence of peroxygen bleach, and (b) a dye transfer inhibition agent such as a polyamine oxide compound. Compositions disclosed in this reference provide effective bleaching performance on fabric stains without unacceptable transfer of dyes between fabrics. However, this reference did not disclose the use of PEIs to enhance stain removal from fabrics in the absence of bleaching compounds. Moreover, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
U.S. Pat. Nos. 6,525,012 and 6,579,839 to Price et al. (and currently owned by Procter and Gamble) disclose liquid laundry detergent formulations that provide enhanced hydrophilic soil cleaning benefits, comprising 0.01 to 20% by weight of a zwitterionic polymer which comprises a polyamine backbone, particularly wherein the degree of quaternization of the polyamine backbone is controlled, and from 0.1% to 7% by weight of a polyamine dispersant. However, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
U.S. Pat. No. 6,964,943 to Bettiol et al. (and currently owned by Procter and Gamble) discloses laundry detergent compositions comprising a mannanase and a cotton soil release polymer, such as a polyethyleneimine, to provide superiod cleaning and soil release performance. However, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
U.S. Pat. No. 7,141,077 to Detering et al. (and currently owned by BASF) discloses a process for wrinkleproofing cellulosic textiles, comprising treating the textiles with a finish comprising one or more water-soluble or water-dispersible hydrophobically modified polyethyleneimines and/or polyvinylamines. However, this reference did not disclose the use of PEIs to enhance stain removal from fabrics in the absence of bleaching compounds. Moreover, this reference did not disclose that at molecular weights above about 25 kDa and/or at concentrations higher than about 2% by weight, PEI polymers actually cause fixation of stains into fabrics, rather than enhancing their removal.
Thus, there remains a need in the art for cleaning compositions suitable for use in laundry, hard surface and/or dishware cleaning applications, that are substantially free of phosphorous-based and peroxygen or chlorine bleach compounds, and that exhibit excellent cleansing and stain removal performance, particularly under harsh water conditions, and particularly when used on traditionally difficult-to-remove stains including but not limited to polyphenolic-based stains such as cherry juice, blueberry juice and red wine, along with tea, coffee and chocolate pudding.